Process for the production of physiologically inert oils



July 25, 1944. E. B. PECK 2,354,540

PROCESS FOR THE PRODUCTION OF PHYSIOLOGICALLY INERT OIL Filed Oct. 31, 1940 SYN THESIS GASiS/ (LA Y( 20415 Q 1; v 51 zfize 921 w I/VERT OIL PRODUCT PRODUCT [DST/LL14 T/ON ZONE Patented July 25,1944

PROCESS FOR THE PRODUCTION OF PHYSIOLOGIOAILY mm'r OILS Edward B. Peck, Elisabeth, N. 1.,

mesne assignments, to Standard Company, a corporation of Delaware assignor, by Catalytic Application October 31, 1940, Serial No. 363,643

Claims. (Cl. 260-4495) The present invention is concerned with the manufacture of valuable hydrocarbon products by the hydrogenation of oxides of carbon. The invention is more particularly concerned with the control of operations of this character for the production of substantially aromatic free and physiologically inert products which are partlcu- I larly adapted for human use in the form of cosmetics, medicinal oils and the like. In accordance with the present invention, products of this character are prepared by the hydrogenation of oxides of carbon utilising a particular catalyst under controlled conditions which are adapted to produce relatively high yields of physiologically inert oil products.

It is well known in the art to prepare physiologically inactive oils having no aromatic constituents by various procedures. One convention a-i method employed, for example, is to treat animal or vegetable oils or the fatty acids derived therefrom by hydrogenation or other methods that remove or change the carboxyl group or unsaturated active groups to inert saturated groups. This procedure is not particularly satisfactory since yields are low and the operations are relatively expensive. It is also known in the art that hydro carbon constituents containing more than one carbon atom in the molecule and various related oxygenated compounds may be obtained by reacting oxides of carbon with hydrogen at elevated temperatures and pressures in the presence of a suitable catalyst and under controlled temperature and pressure conditions. In these operations the conventional operation is conducted in the general temperature range from about 300 F. to about 410 F. In general the operation is' so controlled that the predetermined operating temperature does not vary more than about F. and is usually controlled so that the temperature variance does not exceed about 5 F. Pressures in the general range from about atmospheric to about atmospheres are employed. In these operations a wide variety of catalysts may be employed, as for example cerium, chromium cobalt,

manganese, osmium, palladium, titanium, zinc, iron, and oxides or, other compounds of these meta-ls, as well as mixtures of the same. In operaoxide andhydrogen, preferably in the ratio of one volume of carbon oxide 'to two volumesof hydrogen, arecontacted at about atmospheric or moderate pressures at temperatures from about 360' 1". to about 500 Fs in contact with one of the of reactors with intermediate zones adapted for the condensation of the products formed. The material condensing at atmospheric temperature is largely water and the higher boiling fractions oi the oil. The relatively low boiling fractions of the oil, including most of the hydrocarbon constituents boiling in the motor fuel boiling range, are recovered by an absorption operation or by another suitable process.

In these operationsthe quality and character of the product produced varies considerably with the particular catalyst used as well as upon general operating conditions. When the catalyst comprises an iron catalyst, approximately 70% to 80% of the hydrocarbon product boils below 400 F., theconstituents of which are highly alkyl branched-chain compounds comprising about 60% olefins. When employing a ruthenium cata lyst, the product comprises about 75% to about 80% or high molecular weight saturated parafllns, and is substantially free of aromatic hydrocarbons.

Cobalt and nickel catalysts give intermediate quality products, those from nickel being most parafllnic, and those from cobalt most olefinic.

The quality of the product may be somewhat altered by changing the ratio of carbon monoxide to hydrogen in the feed gases. For example, an increase in the hydrogen will increase the yields of saturated lower molecular weight products. On the other hand, cobalt and nickel catalysts produce small amounts oi unsaturated hydrocarbons, as shown by the refractive index and the distillation-specific gravity relationships.

I have now found that a catalyst which consists of an alloy of nickel containing 10% of cobalt produced by first alloying with aluminum and subsequently dissolving out the aluminum by. treatment with caustic, which when utilized in the hydrogenation of oxides of carbon produces a product, about 40% of which boils above 400' F. and which'is free from aromatic hydrocarbons. Although the yields in employing this catalyst are smaller than those produced in conventional operations, the product contains, substantially no constituents other than highly parafllnic physiological inert oil constituents. The particular fractionfprjoduced in this manner whichisespecifi im eian s olfie.. fl fl" h hfiboi sia whiehls condense with above named or equivalent catalysts at space u of about 1". at atmospheric pressures.

hat

one carbon atom in the molecule.

f My. invention-may be readily understood by reference to the drawing illustrating one modification oi the same. Feed gases comprising carbon monoxide and hydrogen are produced in generator l-and introduced into synthesizing zone 2 by means 01 line 3. synthesizing zone 2 is provided with suitable distributing, heating and cooling means. Zone 2 is also packed with a suitable catalystwhich-for the purpose of descrip: tion is taken to be an alloy of nickel containing 1% cobalt. Operating temperatures are ad- Justed to produce hydrocarbon constituents containing more than one carbon atom in the molecule. a j

The reaction products are withdrawn from reaction zone 2 by means of line ,4, passed through cooler 5 and introduced into separating zone 6. Unreacted constituents are removed from separating'zone 6 by means of line I and passed into a second synthesizing zone 8. synthesizing zone 8 is provided with suitable distributing, heating and cooling means. This zone is packed with a conventional catalyst and operating conditions are adjusted to secure the maximum yield of hydrocarbon constituents containing more than The reacted products are withdrawn from synthesizing zone I by means of line 9, passed through cooling zone I and introduced into separation zone H in which the synthesized products are separated from the unreacted gases.

For purposes of description it is assumed that I this separation is secured by means of an oil absorption operation. The absorption oil is introduced in the upper part of separation zone H by means of line l2 and flows downwardly contacting the upflowin'g gases under conditions to absorb therein the desired constituents. The vaporous undissolved gases are removed overhead from separation zone II by means of line l3 and handled or'further treated in any manner desirable. The absorption oil containing dissolved therein the desired hydrocarbon constituents is removed from separation zone II by means of line l4 and passed into distillation zone IS in which the disso lved hydrocarbon constituents are removed from the absorption oil. The absorption oil free of dissolved hydrocarbons is removed from distillation zone l5 by means of line l6 and recycled to absorption zone II. The hydrocarbon constituents removed from the absorption oil are removed overhead from distillation zone l5 by a means of line I! introduced into cooler l8 and passed to separation zone l9. Uncondensed gases troduced-into separation zone 23 in which the relatively low boiling constituents, are removed overhead by means of line 24 while the desired physiologically inert oil constituents are removed by means of line 25. This product is introduced into treating zone 26 in which it is contacted with an alkali metal hydroxide solution which for purposes of description is assumed to be a sodium hydroxide solution. Fresh sodium hydroxide solution-is introduced into treating zone 20 by means fof line "and the spent solution withdrawn by means of line 28. The treated oil is 'svithdrawnirom treating zone 26 by means of II and passed into clay contacting or equivathe general range from about 5% to about 20% cobalt. Preferred results" are, however, secured when the amount of cobalt present is about 10% based on the quantity of nickel. It is, however, to be understood that small quantities of other promoting substances may be present such as copper or an alkali as, for example, potassium carbonate. The ruthenium similarly may have present a small quantity of copper, the concentration of which is in the range from about 0.5% to about 5.0%.

In accordance with a preferred modification of .the following example is given which should not be construed as limiting the same in any manner whatsoever.

} Example Feed gases comprising hydrogen and carbon monoxide were contacted with a nickel catalyst containing about 10% of cobalt at a temperature of about 400 F. and at about atmospheric pressure. The reaction products removed from the synthesizing zone were cooled to about atmospheric temperature and the condensate separated. The condensate 'was distilled in order to segregate constituents boiling above about 400 F. This product was contacted with an alkali metal hydroxide solution and clay treated. The resulting product had the following inspection: p Y Specific gravity 0.735 at 20 F.

Pour point F 45 p Iodine number 4.4

Olefin content per cent 4 p The process of this invention is not to be limited by any theory or mode of operation but only by the following claims.

I claim:

1. The process'for the production of highly paramnic hydrocarbon oils of high boiling point which comprises passing two volumes of hydrogen with one volume of carbon monoxide over I a skeleton alloy catalyst consisting of nickel and i' -20% cobalt with reference to the nickel at a temperature between 360 F. and 500 F., and at a pressure in the range from about atmospheric to about 20 atmospheres, segregating normally 5 liquid hydrocarbons boiling about 400 F. and

further purifying the same.

2. Theprocess for the production of highly paraflinic hydrocarbon oils of high boiling point which comprises passing two volumes of hydrogen with one volume of carbon monoxide over a skeleton alloy catalyst consisting of nickel and 540% cobalt with reference to thenickel at a temperature between 360 F. and 500 F., and at of oxides of carbon, which comprises passing two volumes of hydrogen with one volume of carbon monoxide in an initial stage at-a temperature in the range from about 380 F. to about 500 F. at a pressure in the range from about 1 to about 20 atmospheres over a skeleton alloy catalyst consisting of nickel and 540% cobalt with reference to the nickel, separating the reaction products 7 and cooling the same whereby a condensate separates, removing said condensate comprising.

highly parafllnlc hydrocarbon oils of high boiling point and passing the cooled gases to a secondary stage,and further reacting said gases in said secondary stage in the presence of a synthesizing catalyst under conditions to secure a maximum yield of hydrocarbon constituents containing more than one carbon atom in the molecule.

4. Process according to claim 1 in which said alloy catalyst consists of nickel containing about 10% of cobalt alloyed therewith.

5. Process in accordance with claim '3, in which said alloy catalyst employed in said initial stage consists of nickel containing about 10% of cobalt alloyed therewith.

. EDWARD B. PECK. 

